Process for treating grass



St te Pa PROCESS FOR TREATING GRASS Sherman Converse, Aiken, S. C.,assignor to Graniteville (CIompany, Gramteville, S. C., a corporation ofSouth 81'0 Illa No Drawing. Application April 10, 1958 Serial N 0.727,553

11 Claims. (Cl. 117-3) 7 This invention relates to the treatment ofgrass which has become discolored or turned brown by reason of drought,disease, cold weather or other causes, and more particularly to thepermanent restoration of a natural life-like appearance to such grassand the protection of such grass from deterioration.

In many sections of the country perennial grasses such 'each winter hasa bad effect on the condition of the peren'mal grass. Treatment of thedormant perennial grass in the manner described herein does not damagesuch grass and has the advantage of eliminating the labor and expense ofwatering, fertilizing and mowing required in the case of Winter grass;In the spring the'n'ew perennial grass shoots come up just as they wouldif the dormant grass had remained untreated.

vGrass, whether perennial or otherwise, may also become discolored fromother causes such as drought or disease and the invention is also usefulin treating such grasses to permanently protect them from' deteriorationthrough mechanical action and to permanently impart thereto a naturalgreen color.

The principal object of the invention therefore is to treat discoloredgrass by the application thereto of a natural green colored protectivecoating such that the treated grass will regain the color and appearanceof living grass and will retain this color and appearance without changeuntil replaced by new growth. This may be accomplished by theapplication to discolored grass of certain aqueous'dispersions offilm-forming, water-insoluble resinous binders containingwater-insoluble coloring matter, whereby the treated grass is not onlygiven a permanent natural green color, but is also permanently coatedwith a tough, flexible, adhesive, cohesive, weather, water and abrasionresistant film which tightly adheres to the grass when the dispersiondries and protects the treated grass from deterioration or crumblingthrough mechanical action.

The terms permanent and permanently as used herein and in the appendedclaims in reference to the length of time the treated grass retains thebenefits of the treatment means that the protective colored film remainson the treated grass until such grass is replaced by newgrowth. Thislength of time varies from a few weeks to several months depending onlocality and weather conditions. These factors do not affect the treatedgrass but only the emergence of the new growth which replaces thetreated grass.

The invention is particularly suitable for the treatment of lawns,cemetery lots, athletic fields, etc. Numerous commercial applicationshave shown that the coating does not change color noticeably over aperiod of'up to six months, does not rub ed on shoes or clothing whichmay come in contact with it, even when Wet, and is not affected by rainor snow or by continued foot traffic.

In order to attain this objective it has been discovered, in accordancewith the invention, that a composition is required such that the film orcoating it produces will meet certain standards of performance withrespect to the following physical properties: water resistance, abrasionresistance, wet and dry crock resistance, adhesion, breaking strengthand elongation, and weather resistance. These properties are determinedby testingfilms formed from the composition on any suitable surface suchas glass or mercury. The tests are performed in accordance with standardtest methods and the results expressed in numerical terms.

The test methods used are as follows:

(1) Water resistance.-,Wate r resistance is measured by the ASTMtentative test method D570-54T for determination of the degree of waterabsorption of plastics. The test is carried out on a 5 mil (.005)film'prepared by coating or spraying the composition on a suitablesurface and'allowing to dry- The film is removed, dried for 1 hour at105 -ll0 C., and weighed. It is then soaked in water for 24 hours at 23C. The film is then removed, all surface water wiped off with adry'cloth and immediately weighed. The increase in weight divided by theoriginal weight gives'the percentage water absorption.

(2) Abrasion resistance-Abrasion resistance is measured by testing a 5mil film prepared as above onthe Taber abraser using a'CS-lO wheel and a500 gram Weight. The number of revolutions required to wear a hole inthe film is ameasure'of the abrasion resistance.

(3) Crack resistance-Crock resistance is measured by testing a 5mil-film on the AATCC crockmeter by the method described .on pages 76 ofthe 1956 Technical Manual and Year Book of the American Association ofTextile Chemists and Colorists. In this apparatus a 2" square of white,bleached cotton cloth (lawns, percales or printed cloths are suitable)is placed on the end of a peg or finger and the peg is rubbed back andforth over the surface of the film 10 times for a distance of about sixinches. For a dry crock test the cloth is dry and for a wet crock testthe cloth is wet with water. The amount of color picked up by the clothis compared with a standard AATCC color transference evaluation chart.This chartconsists of four rows of six'colors each, namely, neutralgray, red, yellow, green, blue and purple. Each row is a different depthranging from a light tint in row 4 to a moderately deep shade in row 1.The amount'of color on the white cloth is compared with the chart andthe degree of fastness' to crocking expressed as a class No. accordingto the row containing the color chip to.

which the stain on the white cloth most closely corresponds. If thischip is in row 1 the crock fastness is in class 1, row 2 is class 2,etc. Class 5 is the best, showing virtually no color transfer to thewhite cloth.

(4) Adhesion.--Adhesion is measured by casting a 5 mil film on glass,marking ofi a' 1-inch wide strip about 5 inches long by cutting with aknife, peeling one end of the strip, placing this end in a clampattached to one arm of a pair of scales, placing weights in a panattached to the other arm of the scales, and determining the weightrequired to pull the strip from the glass a distance of Mt" per minute.In case the breaking strengthof the filmis not sufiicient to overcomethe adhesive force between the film and the glass, a pressure sensitiveadhesive tape 1 inch in width or less may be applied to the top surfaceof the strip of film in order to furnish the necessary tensile strength.a

(5) Breaking strength arid el0ngati0n.Breaking v strength and elongationare determined on a testing utility for its intended purpose.

machine having a pendulum weighing head to measure the load applied tobreak the specimen. A strip of film approximately 5 mils (.005 inch)thick, 5 inches long, and 1 inch wide is used for the test. The strip isplaced in the grips of the tester and the grips moved apart at aconstant rate until the film breaks. The rate of motion of the poweredgrip is 2 inches per minute for films with an ultimate elongation lessthan 100 percent, and 20 inches per minute for films with an ultimateelongation of 100 percent or more. The initial distance between thegrips, or gage length, shall be 1 inch for materials having a totalelongation at break of 100 percent or more and 3 inches for materialshaving a total elongation at break of less than 100 percent. The machineis equipped with a device for indicating the tensile load carried by thespeciman. Breaking strength, or breaking factor, is calculated bydividing the load at break in pounds by the original width of thespecimen in inches and is expressed in pounds per inch.

Elongation is a measure of the elasticity and, to some degree, of theflexibility of the film. Percentage maximum elongation is calculated bydividing the elongation at the moment of rupture of the specimen by theoriginal length of the measured elongating section.

(6) Weather resistance-Weather resistance is determined by exposing a 5mil film in an Atlas twin arc weatherometer. This apparatus is equippedwith two carbon arc lamps and water sprays automatically regulated tospray the test sample for a 9-minute period at 51-minute intervals. Thesample is, therefore, alternately wet and dried. All other conditions ofthe test are in accordance with Method 5004 of Federal Specification.CCC-Tl9lB. This apparatus provides an accelerated test of theresistance of the material to weather exposure by measuring the colorfastness or resistance to fading of the color pigments as shown by thedegree of color change, and also by measuring the resistance of thefilmforming resinous binder to deterioration as shown by a change inappearance or condition of the film brought about by cracking,blistering, or wrinkling, or by bleeding or mechanical loss of color.The degree of weather resistance is expressed as the number of hoursexposure required to produce an appreciable change in color 0 appearanceof the film. V

All-films are dried at room temperature and conditioned for a minimum of24 hours at a temperature of 70 F. and 65% relative humidity, and all ofthe foregoing tests, except the water resistance andweather rev sistancetests, are conducted under these same temperature and humidityconditions.

The water and weather resistance tests are carried out under theconditions described in the foregoing explanations of these testmethods.

The following represents the physical property value limitations, asmeasured by the foregoing test methods, applicable to 5 mil (.005) filmsproduced from compositions which, in accordance with the invention, willproduce satisfactory results in use:

Each one of the physical properties listed above has an effect on thequality of the protective film and its A certain degree of breakingstrength, abrasion resistance, and adhesion is necessary in order thatthe film on the grass will satisfactorily resist removal from the grassby any mechanical action such as being walked on. Also, browned-outgrass tends to be brittle and crumbly and a film having the necessarydegree of strength, abrasion resistance, and

\ soluble fugitive dyestuffs.

broken up by any mechanical action such as being walked on or by theaction of wind and rain. Good crock resistance is necessary to preventthe color from rubbing off on the person or clothing of anyone coming incontact with the colored grass. Good color retention and resistance toweather exposure is necessary in order that the colored glass willretain its original appearance for the desired length of time, A lowdegree of water absorption is required as absorption of water weakensthe film and lowers its tensile strength, abrasion resistance andadhesion.

Several attempts have been made in the past to provide grass coloringcompositions. For instance, Monteith in U. S. Patent No. 2,113,625employs a solution of water- LockIcy et al., in U. S. Patent No.2,714,062 discloses a method of providing a temporary coloration by theuse of a water-soluble dyestuff and a water-soluble binder incombination with a fertilizer mixture. Gardner et al., in U. S. PatentNo. 2,786,821 discloses certain combinations of water-soluble dyestuffs,water-insoluble pigments and aqueous dispersions of water-insolublebinders.

None of these compositions meet the minimum physical property values ofthe herein described invention and, therefore, do not fulfill itspurpose, namely, providing on grass a permanent, tough,flexible,cohesive, adhesive, weather, water, and abrasion-resistantnatural greencolored film which will not change in color, will not rubofi on shoes or clothing which may come in contact with it, is notafiected by rain or slow, and which protects the treated grass fromdeterioration by continued foot traflic.

it has been found, according to the invention, that cer taincompositions of aqueous dispersions or emulsions of certainfilm-forming, Water-insoluble resins used as the binder or vehicle forcertain water-insoluble coloring matter, such as pigments or certain oiland solvent soluble dyestuffs or combinations thereof, fulfill theminimum requirements with respect to the physical properties listedabove.

Resinous binders which may be employed include aqueous dispersions oremulsions of interpolymers produced from mixtures of variouspolymerizable acrylic monomers such as methyl acrylate, ethyl acrylate,propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate,sec.

.butyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate,

methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert.butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid,ammonium methacrylate. Also, aqueous dispersions or emulsions ofpolymers or r v interpolymers produced from polymerizable monomers suchas vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride,butadiene, styrene, acrylonitrile, dibutyl maleate, ethyl acrylate ormixtures thereof; and aqueous dispersions or emulsions of interpolymersproduced from mixtures of these monomers with any of the above mentionedacrylic monomers. Also aqueous emulsions of alkyd resins andoil-modified alkyd resins, in cluding oxidizing and non-oxidizing, long,medium or short oil, either cut with solvents such as toluol, xylol ormineral spirits or in 100% solids form, may be used as the sole binderor in admixture with the above and below mentioned resinous binders.Other binders which would not be suitable as the sole binder but whichmay be used in varying amounts with the above mentioned binderdispersions are aqueous dispersions of coumarone-indene, phenolic,chlorinated diphenyl, rosin, and modified rosin, ester gum, naturalresins and polymerized petroleum hydrocarbon resins.

An example of a preferred binder, chosen because of its desirablephysical properties including stability to both storage and agitation inaddition to the other desirable physical properties enumerated herein,is an aqueous dispersion (46% solids) of interpolymer produced byemulsion polymerization of the. following mixture of mono- -mers; ethylaerylate-66%,' 'methyl. methacrylate- 32.75%, methacrylic acid- 1.25%.This is the binder employed in Examples 1, 2, 8, 9,, and 11 herein andit is derived from a solution of 25 parts of anoctylphenoxypolyethoxyethanol having about 30 ether groups in 1000 partsof water to which is added with stirring a mixture of 280 parts of ethylacrylate, 140 parts of methyl methacrylate, and 5.5 parts of methacrylicacid. The resulting mixture is cooled to C. A solution of 0.5 part ofammonium persulfate in 1.5 parts of water is then added, followed byaddition of'a solution of 0.6 part of sodium hydrosulfite in six partsof water. Stirring is continued.. In a few minutes the temperature ofthe mixture begins to rise and continues to rise, reaching about 65 C.in a half hour. After five minutes the mixture is cooled to about 15 C.There are now added 35 parts of the same octylphenoxypolyethoxyethanol,315 parts of ethyl acrylate, 155 parts of methyl methacrylate, 6 partsof methacrylic acid, a solution of 0.6 part of ammonium persnlfate in1.5 parts of water, and 0.8 part of sodium hydrosulfite in six parts ofwater. In a short time the temperature of the mixture rises, a maximumof about 65 C. again being reached. Stirring is continued for an hourand then while the batch is cooled to 30C., ammonium hydroxide solutionis added until a pH of 9.5 is reached.' The resulting product is adispersion of an interpolymer of ethyl acrylate, methylmethacrylate,-and methacrylic acid in over a 99% yield.

Pigments, which are of course water-insoluble, employed in the coatingcomposition may be .any of the chrome yellows, cadmium yellows, Hansayellows, which are acetoacetic arylide couplings with substitutedanilines, like 4-chloro 2-nitro-aniline, or orthonitraniline, amongothers, Benzidine yellows, which arecouplings between dichlorobenzidineor acetoacetic acylides, such as the aceto-acetic-anilide, -ortho chloroanilide, Phthalocyanine blue, which is a copper or tin-copperphthalocyanine, Phthalocyanine green, which is a chlorinated copperphthalocyanine, and Chromium. Oxide greens. In the coating formulations,these pigments are employed in the form of water-dispersible pasteswhich may or may not contain emulsifiable oil or resinous binders.

In order to 'maintain good pigment dispersions thus preventing too greata degree of fluocculation and settling, wetting agents, dispersingagents and thickening agents may be used. In order to 'promote fasterfilm formation and improve film integrity, various liquids having asolvent action on the particular resin present, may be used. In order toimprove pigment wetting and thus derive maximum color value from thepigments various emulsifiableoils and oil-containing resins such asalkyds, and also plasticizers and solvents may be used.

Other water-insoluble coloring matter which may be employed in thecoating composition are oil or solvent soluble dyestuffs, but notwater-soluble dyestuffs, and these may be used in addition to or inlieu' of pigments.

Among the thickening agents whichmay be employed are included methylcellulose, sodium carboxymethyl cellulose, hydroxyethyl cellulose,sodium acrylate, and ammonium polyacrylate.

As dispersing agents there may be employed Calgon (sodiumhexametaphosphate), Daxad (sodium salt of polymerized alkyl naphthalenesulphonic acid) and ammonium caseinate.

As wetting agents, where they are desirable, there may be employedAerosol OT '(dioctyl sodium sulfosuccinate),

'Santomerse D (decyl benzene sodium sulfonate) and various soaps such asthose formed through the interreaction of oleic acid and morpholine-orammonia.

It will be apparent to those skilled in the art that mixtures of two ormore resins or resinous binders in the coating formulations arecontemplated, as well as mixtures of pigment pastes to give the desiredcolor shade. Moreover, mixtures of thickening agents as well as mixturesof wetting and dispersing agents are contemplated.

It=should beunderstood. that the success of the coating 36 oz. ammoniumcomposition is not dependent upo'nthe juse-of any particular resinousbinder, nor is it dependent upon the use of any particular coloredpigment, butrather upon the use of such binders and pigments andauxiliary agents, if any, which, when properly formulated, produce afilm having the aforesaid physical properties. Stated differently, theuse of any water-insoluble resinous binder and any desiredwater-insoluble coloring matter is contemplated just so long as thecombination thereof forms a film having the physical propertiesdescribed above. Other resinous binders and color pigments will occur tothose skilled in the art. I

The following arespecific examples of compositions which have producedexcellent results in a large number of commercial applications:

Example 1 6 /2 ozs/Chromium Oxide Paste (dispersion of inorganic pigmentin water-68% solids) oz. ammonium polyacrylat'e (emulsion thickener- 30%solids) if; 8;: 212213 5: (wetting and dispersing agent) 3 lbs. 12 ozs.water Total weight8 lbs. 6 ozs. Total volume-l gallon. Weight of dryso1ids2 lbs. 1.75 ozs. Percent dry solids25%.'

The total weight of binder and pigment solids in this concentrate is 2pounds 1.3 ounces and the ratio of binder solids to pigment solids is1.6 to 1.0. When the concentrate was diluted toa sprayable consistency,in this case in the proportion of 1 part concentrate to 5 parts water byvolume, and applied to 1500 square feet of dormant grass, 6 gallons ofspray mix (1 gallon of concentrate plus 5 gallons of water) deposited2.2 ounces of solid material per square feet. This produced a pleasingnatural grass color which remained unchanged throughout the dormancyperiod of four months.

" 7 Film formed from the above concentrate exhibited the followingphysical properties when subjected to the tests previously describedherein: V

2 lbs. 9 ozs. aqueous dispersion (46% solids) of interpolymer producedby emulsion polymerization of the following mixture of monomers: ethylacrylate-66%, methyl methacrylate-32%%, methacrylic acid- 114% 9% ozs.Phthalocyanine Green P a ste (CI-74260, 58% solids, composed of 30%pigment solids and 28% binder solids) 17% ozs. Hansa Yellow G Paste(CI-11680, dispersion of organic pigment in water-40% solids)polyacrylate emulsion thickener (30% 7 3% ozs. methyl cellulose, 4000up. (1% solution) 9a 02. ammonia 4 lbs. 2 cm. water Total Weight-8 lbs.ozs. Total volu'me--1 gallon. Weight of dry solidsl lb. 15.4 ozs.Percent dry solids22%.

The total weight of binder and pigment solids in this concentrate is 1pound 15.2 ounces and the ratio of binder solids to pigment solids is2.2 to 1.0. When diluted with 5 gallons of water and applied to 1500square feet of grass the weight of solid material deposited per 100square feet was 2.1 ounces. This also produced a pleasing natural grasscolor which remained unchanged over a period of four months.

Test results on the above formulation are as follows:

The Phthalocyanine Green Paste in the foregoing example is composed of:

30% Phthalocyanine Green pigment 17.5% partially neutralized ester oflinseed oil (100% solids) V 17.5% non-drying 'phthalic alkyd resin (60%solids in xylol) 35% methyl Cellosolve (ethylene glycol mono methylether).

This composition emulsifies easily in water containing an alkali such asammonia and gives better color value than conventional water pastes". Itis added to the Water and ammonia before being mixed with the remainderof the concentrate.

Other formulations which have been tested and found to produce entirelysatisfactory results are as follows:

Example 3 2 lbs. 11 ozs. emulsion copolymer of 62.5% vinyl acetate and37.5% dibutyl maleate (55% solids) 7 /2 ozs. Phthalocyanine Green Paste(CI-74260, dispersion of organic pigment in water-35% solids) ozs. HansaYellow G Paste (CI-41680, dispersion of organic pigment in water'-40%solids) 6% ozs. Chromium Oxide Paste (dispersion of inorganic pigment inwater--68% solids) I Ms oz. ammonium polyacrylate emulsion thickener(30% solids) 1 oz. ammonia 4 lbs. 5% ozs. water Total weight-23 lbs. 14/8 ozs. Total volume-1 gallon.

Weight of dry solids-2 lbs. 4% ozs. Percent dry solids26%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 2.4ounces. Ratio of binder solids to pigment solids is 1.8 to 1.0.

Test results on film formed from the above formulation are as follows:

Water resistance 15% absorption. Abrasion resistance 3000 revolutions.Crock resistance, cl'a'ss:

Dry, 3.

Wet, 3. Adhesion 8 ounces. Breaking strength 4 pounds per inch.Elongation 200%. Weather resistance 900 hours.

Exam le 4 2 lbs. 11 ozs. 40% butadiene-60% styrene copolymer late): (50%solids) 7% 02s. Phthalocyanine Green Paste (CI-74260, dispersion oforganic pigment in Water-35% solids) 15 ozs. Hausa Yellow G Paste(CI-11680, dispersion of organic pigment in water40% solids) 6% ozs.Chromium Oxide Paste (dispersion of inorganic pigment in water68%solids) /3 ozs. ammonium polyac'rylate emulsion solids) 4 lbs. 3% 025.water 1 oz. ammonia Total Weight-3 lbs. 13% ozs. Total volume-1 gallon.Weight of dry solids-2 lbs. 2 /2 ozs. Percent dry solids-'24%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 2.3ounces. Ratio of binder solids to pigment solids is 1.6 to 1.0.

Test results on film from the above formulation show the following:

Water resistance a 16% absorption. Abrasion resistance -a 525revolutions. Crock resistance, class:

Dry, 3.

Wet, 2. Adhesion n. 2 /2 ounces. Breaking strength 2 pounds per inch.Elongation 600%. Weather resistance 300 hours.

Example 5 2 lbs. 12% ozs. aqueous emulsion of soya oil modified glycerylpht'nalate alkyd resin-24% phthalic anhydride, 65% oil (46% solids) 7 /2ozs. Phthalocyanine Green Paste (CI74260, dispersion of organic pigmentin water% solids) 15 ozs. Hansa Yellow G Paste (Cl-11680, dispersion oforganic pigment in water-40% Solids) 6 /2 ozs. Chromium Oxide Paste(dispersion of inorganic pigment in water'6 8% solids) 02. ammoniumpolyacrylate emulsion (30% solids) oz. ammonia A; 02. drier (emulsion ofcobalt naphthenate-% solids) Total weight-4 lbs. 11 ozs. Total volume-l6gallon. Weight of dry solids-2 lbs. 2 ozs. Percent dry solids- Dilutedto a sprayable consistency and applied to 1500 square feet of grass, theweight of solid material deposited per 100 square feet is 2.2 ounces.Ratio of binder solids to pigment solids is 1.6 to 1.0.

Test results on the above are:

Water resistance absorption.

Abrasion resistance revolutions. Crock resistance, class:

Dry,-2.

Wet, 2.

. Adhesion 10 ounces.

Breaking strength 1 pounds per inch. Elongation 25%. Weather resistance100 hours.

Example 6 2 lbs. 11 ozs. aqueous dispersion of 40% vinyl chloride, 40%vinylidene chloride, 20% 2-ethylhexyl acrylate copolymer (52.7 solids) 7/2 ozs. Phthalocyanine Green Paste (CI-74260, dis- Persian of organie'igment in water- 35% solids).

1502s. Hausa Yellow G Paste'(CI-l680, dispersion of organic pigmeht inwater-40% solids) 6 ozs. Chromium Oxide Paste (dispersion of inorganicpigment in water-68% solids) /8 oz. ammonium polyacrylate emulsion (30%solids) 4 lbs. 8% ozs. water 1 oz. ammonia Total weight-9 lbs. 1 /2 ozs.Total volume1 gallon. Weight of dry solids-2 lbs. 4% ozs. Percent drysolids-25%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 2.3ounces. Ratio of binder solids to pigment solids is 1.7 to 1.0.

Test results on film from the above formulation show the following:

Water resistance 10% absorption. Abrasion resistance 3000 revolutions.Crock resistance, classz.

Dry, 4. Wet, 2. Adhesion 2 ounces. Breaking strength 8 pounds Elongation200%. Weather resistance 150 hours.

Example 7 2 lbs. aqueous dispersion of polyethyl acrylate-50% solids 6%ozs.v Phthalocyanine Green Paste (CI-74260, dispersion of organicpigment in water-35% solids) 13% ozs. Hansa Yellow G Paste (CI-11680,dispersion "of organic pigment in water-40% solids) 6 ozs. ChromiumOxide Paste (dispersion of inorganic pigment in water--68% solids) 4lbs. 13 ozs. methyl cellulose, 4000 cp. (1% solution) 1% ozs. ammonia 1/2 ozs. oleic acid Total weight-S lbs. 10% ozs. Total volume-1 gallon.

Weight of dry solidsl lb. 14% ozs. Percent dry solids22%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 1.9ounces. Ratio of binder solids to pigment solids is 1.3-1.0.

Test results on the above formulation are as follows:

Water resistance 150% absorption. Abrasion resistance 75 revolutions.Crock resistance, class:

Dry, 4.

Wet, 2. Adhesion 1% ounces. Breaking strength pound per inch. Elongation3000%. Weather resistance 500; hours.

Example 18 Total weight-8 lbs. 12% ozs. Total volume-i gallon.

Weight of dry solids-1 lb. 7 /2 ozs. Percent dry solidsl6%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per square feet is 1.5ounces. Ratio of binder solids to pigment solids is .77l.0.

Test results on the above formulation are as follows:

Water resistance 35% absorption. Abrasion resistance 250 revolutions.Crock resistance, class:

Dry, 3.

Wet, 2. Adhesion 6 ounces. Breaking strength 2 pounds. ElongationWeather resistance 250 hours.

Example 9 2 lbs. 11 ozs. aqueous dispersion (46% solids) of interpolymerproduced by emulsion polymerization of the following mixture ofmonomers: ethyl acrylate 66 methyl methacrylate-32% methacrylic acid--1%% 9% ozs. Phthalocyanine Green Paste (CL-74260, 58% solids, composedof 30% pigment solids and 28% binder solids) 17% ozs. Hansa Yellow-GPaste (CI-11680, dispersion of organic pigment in water -40% solids)ozs. ammonium polyacrylate emulsion (30% solids) /2 oz. ammonia 4 lbs. 3ozs. water Total weight-8 lbs. 10 ozs. Total volume-1 gallon. Weight ofdry solids-2 lbs. Percent dry solids23%.

Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 2.0ounces. Ratio of binder solids to pigment solids is 2.3 to 1.0.

Test results on the above formulation are as follows:

Water resistance 30% absorption. Abrasion resistance 2000 revolutions.Crock resistance, class:

Dry, 4.

Wet, 3. Adhesion 3 ounces. Breaking strength 2% pounds per inch.Elongation 800%. Weather resistance 900 hours.

The Phthalocyanine Green Paste in the foregoing example is composed of:

30% Phthalocyanine Green pigment 17.5% partially neutralized esterof'linseed oil (100% solids) 17.5% non-drying phthalic alkyd resin (60%solids in xylol) 35% methyl Cellosolve (ethylene glycol mono methylether).

This composition emulsifies easily in water containing an alkali such asammonia and gives better color value than conventional water pastes. Itis added to the water and ammonia before being mixed with the remainderof the concentrate.

Example 10 p 5 lbs. 9 ozs. aqueous dispersion (46% solids) ofinterpolymer produced by emulsion polymerization of the followingmixture of monomers: ethyl acrylate- 66%, methyl methacrylate-3234methacrylic acid 1%% statute Total weight-8 lbs. 15% ozs. Total volume-1gallon. Weight of dry solids3 lbs. 6 ozs. Percent dry solids-- Dilutedto a sprayable consistency and applied to 1500 square feet of grass, theweight of solid material deposited per 100 square feet is 3.6 ounces.Ratio of binder solids to pigment solids is 3.1 to 1.0.

Test results on the above formulation are as follows:

Water resistance 20% absorption Abrasion resistance 5000 revolutionsCrock resistance, class:

Dry, 4.

Wet, 3. Adhesion 2% ounces. Breaking strength 5 pounds per inch.Elongation l350%. Weather resistance 1500 hours.

Example 11 2 lbs. 11 ozs. aqueous dispersion (46% solids) ofinterpolymer produced by emulsion polymerization of the followingmixture of monomers: ethyl acrylate66%, methyl methacrylate-32%%,methacrylic acid- 1%% ozs. Phthalocyanine Green Paste (CI-74260, 58%

solids composed of 30% pigment solids and 28% binder solids) 14 ozs.Benzidine Yellow G Paste (CI-21090, dispersion of organic pigment inwater40% solids) /8 oz. ammonium polyacrylate emulsion (30% solids) /s02. ammonia 4 lbs. 6 ozs. water Total weight-8 lbs. 9% ozs. Totalvolume-1 gallon. Weight of dry solids-1 lb. ozs. Percent dry solids-Diluted to a sprayable consistency and applied to 1500 square feet ofgrass, the weight of solid material deposited per 100 square feet is 2.1ounces. Ratio of binder solids to pigment solids is 2.6 to 1.0.

Test results on the above formulation are:

Water resistance 5% absorption. Abrasion resistance 2000 revolutions.Crock resistance, class:

Dry, 3.

Wet, 3. Adhesion 2% ounces. Breaking strength 2% pounds per inch.Elongation 900%. Weather resistance 500 hours.

The Phthalocyanine Green Paste in the foregoing example is composed of:

% Phthalocyanine Green pigment 17.5% partially neutralized ester oflinseed oil (100% solids) 17.5% non-drying phthalic alkyd resin (60%solids in xylol) methyl Cellosolve (ethylene glycol mono methyl ether)This composition emulsifies easily in water containing an alkali such asammonia and gives better color value than conventional water pastes. Itis added to the water and ammonia before being mixed with the remainderof the concentrate. Although this composition of Phth'alocyanine GreenPaste is described only in connection with Examples'Z, 9 and 11 it is tobe understood that it may be employed in any of the other examples or inany formulation falling within the scope of the appended claims, makingsuitable allowance for the variations in pigment and'binder solids Wherenecessary. 7

From the data given after each of the above formulation examples thepercentage of pigment and binder solids in each example and the rangesof both pigment and binder solids applied per square feet over a 1500square foot area may be calculated. These ranges are as follows:

Pigment solids-.57 (Example 11) to .87 (Examples 1,

3-6, 8 and 10) ounces per 100 square feet.

Binder solids-.67 (Example 8) to 2.7 (Example 10) 1 ounces per 100square feet.

The percentage of pigment solids ranges from 56% (Example 8) to 24%(Example 10) and the percentage of binder solids ranges from 44%(Example 8) to 76% (Example 10). The ratio of binder solids to pigmentsolids is given for each formulation example and varies fromapproximately .75 to 1 (Example 8 has ratio of .77 to l) toapproximately 3 to 1 (Example 10 has ratio of 3.1 to 1).

It has been found that the above ranges are those which producesatisfactory results from the standpoint of color and performance.

The recommended degree of dilution given for each of the concentrates inthe above formulation examples is that which produces a total volume of6-12 gallons. The amount of satisfactory coverage depends on the typeandcondition of the grass to be treated as well as on the 'shade desired,and dilution of the concentrate within this range gives satisfactoryresults when applied to an area of from 1200 to 1800 square feet. Ifsubstantially less than 6 gallons is used the quantity of liquid willnot be suflicienbto cover the desired area uniformly. If substantiallymore than 12 gallons is used the quantity of liquid is more than can beheld by the grass and consequently some of .it will run off the grass tothe ground and be wasted.

The preferred volume for a concentrate containing the right amount ofsolids for application to 1200-1800 square feet (after dilution) is onegallon. The principal reason for this particular volume is that it makesa low viscosity concentrate which mixes easily with the diluting water.A lower volume concentrate with a higher percentage of solids can bemade as shown in Example 5.

The maximum practical amount of both thickener and wetting agent is 5%.Therefore, broad formulations showing workable variations are asfollows:

1. Example 8:

51-56% pigment solids 39-44% binder solids 5-0% thickener solids 50%wetting and dispersing agent solids 2. Example 10:

22-24% pigment solids 68-76% binder solids 5-0% thickener solids 5-0%wetting and dispersing agent solids The optimum ratio of presently knownbinder solids to presently known pigment solids is approximately 2:1. Asstated above, satisfactory results may be obtained by a ratio of bindersolids to pigment solids in the range of approximately 0.75:1 toapproximately 3.0:1. The preferred ratio of presently known bindersolids to presently known pigment solids produces a coating compositionwhich will provide a film having physical properties ideally suited tothe treatment of grass for accomplishing the stated objection of theinvention.

It will be noted that the properties of the different formulationexamples are due to the composite efiect of the various components ofthe formulation. The type and amount of binder has the greatest effecton the physical properties. Variations in abrasion resistance, adhesion,and tensile strength and elongation are for the most part due to adifference in the binder used. Crock resistance and weather resistancealso vary with the binder used. Decreasing the ratio of binder solids topigment solidsresults in a general decrease in quality. Elongation,abrasion resistance, weather resistance and crock resistance arelowered. Increasing the proportions of binder solids to pigment solidshas the opposite efiect. It is evident, of course, that some binders aresuperior to others and, therefore, produce equal or better results atlower ratios. For example, the film produced by the formulation ofExample 7, which has a 1.3-to 1.0 ratio of binder solids to pigmentsolids, has the minimum allowable value for. several physicalproperties, namely water absorption, abrasion resistance, adhesion, wetcrock and tensile strength. On the other hand, the film produced by theformulation of Example 8, which has a different binder, has physicalproperty values above the allowable minimum except for the wet crockrequirement, although it has a binder solids to pigment solids ratio ofonly .77 to 1.0.

Use of inferior pigments, that is, less light-fast pigments results in adecrease in weather resistance due to poorer color retention. The amountand type of thickener and Wetting and dispersing agents used affects thecrock resistance and water resistance. Their effect on crock resistanceis due to their action in assisting the binder to form a protective filmaround the pigment particles. Their effect on water resistance is due totheir watersensitivity.

Films having a high elongation tend to have low abrasion resistancebecause such highly elastic, flexible films are soft and, therefore,have less resistance to abrasive action than harder, less elastic films.On the other hand, some films with low elongation have lowabrasionresistance, not because they are .soft, but because they are brittle anddevelop holes by cracking when subjected to abrasive action, rather thanby wearing through.

,It will be noted from the test data on the various formulations givenin the examples that there is quite a wide variation in the values forsome of the physical properties. For example, elongation runs from 25%to 3000% and breaking strength from 1% lbs. to 8 lbs.' Elongation andbreaking strength bear a certain relation to each other in that, as arule, the greater the elongation the lower the breaking strength andvice versa. The greater the elongation the more elastic and flexible thefilm, and .the lower the elongation the more brittle and rigid the film.A film with a low breaking strength may be entirely satisfactory if ithas sufficient elongation in that when it is subjected to stress it willgive or'stretch rather than break and when the stress is removed it willrecover its original position. As will be noted from the formulationexamples, decreasing the ratio of binder to pigment lowers theelongation and increases the breaking strength in some cases.

Treatment of discolored grass with a coating having the lowest value foreach physical property shown in the examples would be entirely practicaland satisfactory for'the permanent coloring and protection of discoloredgrass.

This application is a continuation-in-part of application Serial No.582,647, filed May 4, 1956, and now abandoned.

What is claimed is:

l. A process for treating discolored grass to impart a permanent colorto it and protect it from deterioration until the discolored grass isreplaced by new growth which comprises the application to such grass ofa protective colored film formed from an aqueous dispersion of afilm-forming, water-insoluble resinous binder colored solely bywater-insoluble coloring matter, the film from which in a '5mil (0.0057)thickness has-the followirig physical properties vvhen tested inaccordance with procedures described herein: (1) Water resistance-motover 150% water absorption; (2) abrasion resistance-not less than 75'revolutions; (3) crock resistance-class '2 or better; (4) adhesion notless than 1 /2 ounces; (5) breaking strengthnot less than pound; (6)elongationnot less than 25%; and (7) weather resistance-- not less thanhours.

2. A process for treating discolored grass which comprises the steps oftreating it with an aqueous dispersion of a film-forming,water-insoluble resinous binder colored solely by water-insolublecoloring matter wherein the ratio of binder solids to coloring mattersolids is in the range of approximately 0.75:1 to approximately 3.0:1,the film from which in a 5 mil (0.005") thickness has the followingphysical properties when tested in accordance with procedures describedherein: (1) Water resistance-not over water absorption; (2) abrasionresistance-not less than 75 revolutions; (3) crock resistanceclass 2 orbetter; (4) adhesion-mot less than 1 /2 ounces; (5) breaking s trength-'not less than pound; (6) elongationnot less than 25%; and (7)weather resistance-not less than 100 hours, and allowing the dispersionto dry through evaporation of its water content whereby a protectivecolored film tightly adheres to the treated grass to" impart a permanentcolor to it and protect the treated grass from deterioration until it isreplaced by new growth.

3. A process for treating discolored grass to impart a permanent colorthereto and provide protection from deterioration untilthe'treated grassis replaced by new growth, said process comprising applying to thediscolored grass a pigmented,'aqueous dispersion of a film-forming,water-insoluble, resinous binder, said aqueous dispersion having asolids content consisting essentially of from about 39% to 76% resinousbinder solids, from about 56% to 22% pigment solids, from about 0% to 5%thickening agent and from about'0% to 5% wetting and dispersing agent,all of said percentages being expressed in terms of weight. 7

4. A process for treating discolored grass to impart a permanent colorthereto and, provide protection from deterioration until the treatedgrass is replaced by new growth, said process comprising applying to thediscolored grass a pigmented, aqueous dispersion of a film-forming,water-insoluble, resinous binder wherein the ratio of binder solids topigment solids is in the range of from about 0.75:1 to 3.0:1; saidaqueous dispersion having a solids content consisting essentially offrom about 39% to..76% resinous binder solids, from about.56% to 22%pigment solids; from about-0% to 5% thickening agent and from about 0%to 5% wetting and dispersing agent, all of said percentages beingexpressed in terms of weight. a 5. A process for treating discoloredgrass to impart a permanent color thereto and provide protection fromdeterioration until the treated grass is replaced by new growth, saidprocess comprising applying to the discolored grasss a pigmented,aqueous dispersion of a film-forming, water-insoluble vinyl resinwherein the ratio of vinyl resin solids to pigment solids is in therange of from about 0.75:1 to 3.021, said aqueous dispersion having asolids content consisting essentially of from about 39% to 76% vinylresin, from about 56% to 22% pigment solids, from about 0% to 5%thickening agent and from about 0% to 5% wetting and dispersing agent,all of said percentages being expressed in terms of weight.

6. A process for treating discolored grasss to impart a permanent colorthereto and provide protection from deterioration until the treatedgrass is replaced by new growth, said process comprising applying to thediscolored grass a pigmented, aqueous dispersion of a film-forming,water-insoluble, acrylic resin wherein the eroes ratioof acrylic resinsolids to pigment solids is in the range of from about 0.75:1 to 3.0.11,said aqueous dispersion having a solids content consisting essentiallyof from about 39% to 76% acrylic resin, from about 56% to 22% pigmentsolids, from about to thickcning agent and from about 0% to 5% wettingand dispersing agent, all of said percentages being expressed in termsof weight. g

7. A process for treating discolored grass to impart a permanent colorthereto and provide protection from deterioration until the treatedgrass is replaced by new growth, said process comprising applying to thediscolored grass a pigmented, aqueous dispersion of a filmforming,water-insoluble, oil modified phthalic alkyd resin wherein the ratio ofalkyd resin solids to pigment solids is in the range of from about0.75:1 to 3.0:1, said aqueous dispersion having a solids contentconsisting essentially of from about 39% to 76% alkyd resin, from about56% to 22% pigment solids, from about 0% to 5% thickening agent and fromabout 0% to 5% wetting and dispersing agent, all of said percentagesbeing expressed in terms of weight.

8. A process for treating discolored grass to impart a permanent colorthereto and provide protection from deterioration until the treatedgrass is replaced by new growth, said process comprising, applying tothe discolored grass a pigmented, aqueous dispersion of a filmforming,thermoplastic, water-insoluble resinous binder composed of at least onevinyl resin, the ratio of binder solids to pigment solids being withinthe range of from about 0.75:1 to 3.0: said aqueous dispersion having aabout 56% to 22% pigment solids; from about 0% to 39% to 76% resinousbinder solids, from about 56% to 22% pigment solids; from about 0% to 5%thickening agent and from about 0% to 5% wetting and dispersing agent,all of said percentages being expressed in terms of weight.

.9. A process for treating discolored grass to impart a permanent colorto it and protect it from deterioration until the discolored grass isreplaced by new growth which comprises the application to such grass ofa.

protective colored film formed from an aqueous dispersion of afilm-forming, water-insoluble resinous binder, a film from which. in a 5mil (0.0057) thickness has the following physical properties when testedin accordance with procedures described herein:

(1) Water resistance-not over 150% water absorption; i (2.) Abrasionresistance-not less than'75 revolutions; (3) Breaking strerigth-not lessthan pound; (4) Adh'esion--not less than 1 /2 ounces; and (5) Weatherresistance-not less than 100 hours.

10. A process for treating discolored grass to impart a permanent colorthereto and provide protection from deterioration until the treatedgrass is replaced by '16 new growth, said process comprising applying tothe discolored grass a pigmented, aqueous dispersion of a film-forming,water-insoluble, resinous binder, said binder consisting of a mixture ofresins, the film from which in a 5 mil (0.005) thickness has thefollowing physical properties when, tested in accordance with proceduresdescribed herein:

(1) Water resistancenot over 150% water absorption;

(2) Abrasion resistance-not. less than revolutions;

(3) Dry crock resistanceclass 2 or better;

(4) Adhesion-not less than 1 /2 ounces;

(5) Breaking strength-not less than pound;

(6) Elongation not less than 25%; and

(7) Weather resistancenot less than hours.

11. A process for treating discolored grass to impart a permanent colorto it and protect it from deterioration until the discolored grass isreplaced by new growth which comprises the application to such grass ofa protective colored film formed from an aqueous dispersion of afilm-forming, water-insoluble resinous binder, a film from which in a 5mil (0.005") thickness has the following physical properties when testedin accordance with procedures described herein: (1) Water resistancenotover water absorption; (2) Abrasion resistancenot less than 75revolutions; (3) Breaking strength-not less than /1 pound; (4) Dry crockresistanceclass 2 or better; and (5) Weather resistance-not less than100 hours.

References Cited in the file of this patent UNITED STATES PATENTS GreatBritain Feb. 13, 1939 OTHER REFERENCES I Publicationz. Parker,Fundamental Considerations, Latex Paints published October 1952 inofficialDigest of Federation of Paint and vVarnish Production Clubs, No.333,. pages 700 through 709.

Payne: Latex Paints" published October 22, .1953, in Paint, Oil andChemical Review, vol. 1.16, No. 22, pages 14, 16, 18, 20, 22, 42, 44,45, 46, 48, 49.

UNITED STATES'PATENT OFFICE CERTIFICATE OF goRREcTIoN Patent No.2,870,037 v January 20, 1959 Sherman Converse It \is hereby certifiedthat error eppeare in the printed epecificeticn of the above numberedpatent requiring correction and. that the acid Letters Patent shouldread as corrected below.

Column 4, line 30, for "slow" read snow column 5, line 43, for"fluocculation" read flocculation column 6, lines 53 to 58 should appearas shown below instead of as in the patent Water resistance 12.5%absorption.

Abrasion resistance- 2200 revolutions.

Croiok y esistance, class:

, Wet, 3.

Adhesion 1% ounces.

column 12, line '73, for "objection" read i-.-- object column 15, lines32;; and 33, for "about 56% to 22% pigment sol-ids; from about 0% to 39%to 76% resinous binder solids, read solids content consistingessentially of from about 39% to 7 6% resinous binder solids,

Signed and-sealed this 12th day of May 1959.

(SEAL) Attest:

KARL H. AXLINE' ROBERT C. WATSON Attesting Ofiicer Commissioner ofPatents

4. A PROCESS FOR TREATING DISCOLORED GRASS TO IMPART A PERMANENT COLORTHERETO AND PROVIDE PROTECTION FROM DETERIORATION UNTIL THE TREATEDGRASS IS REPLACED BY NEW GROWTH, SAID PROCESS COMPRISING APPLYING TO THEDISCOLORED GRASS A PIGMENTED, AQUEOUS DISPERSION OF A FILM-FORMING,WATER-INSOLUBLE, RESINOUS BINDER WHEREIN THE RATIO OF BINDER SOLIDS TOPIGMENT SOLIDS IS IN THE RANGE OF FROM ABOUT 0.75:1 TO 3.0:1; SAIDAQUEOUS DISPERSION HAVING A SOLIDS CONTENT CONSISTING ESSENTIALLY OFFROM ABOUT 39% TO 76% RESINOUS BINDER SOLIDS, FROM ABOUT 56% TO 22%PIGMENT SOLIDS; FROM ABOUT 0% TO 5% THICKENING AGENT AND FROM ABOUT 0%TO 5% WETTING AND DISPERSING AGENT, ALL OF SAID PERCENTAGES BEINGEXPRESSED IN TERMS OF WEIGHT.